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WO2007026018A1 - Solutions d'hydrure d'aluminium et de lithium - Google Patents

Solutions d'hydrure d'aluminium et de lithium Download PDF

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Publication number
WO2007026018A1
WO2007026018A1 PCT/EP2006/065919 EP2006065919W WO2007026018A1 WO 2007026018 A1 WO2007026018 A1 WO 2007026018A1 EP 2006065919 W EP2006065919 W EP 2006065919W WO 2007026018 A1 WO2007026018 A1 WO 2007026018A1
Authority
WO
WIPO (PCT)
Prior art keywords
lialh
methf
solution
hydrocarbon
toluene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2006/065919
Other languages
German (de)
English (en)
Inventor
Uwe Lischka
Alexander Murso
Ulrich Wietelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Priority to CN200680040697.9A priority Critical patent/CN101300192B/zh
Priority to EP06793144A priority patent/EP1924524B1/fr
Priority to US11/991,132 priority patent/US8840805B2/en
Publication of WO2007026018A1 publication Critical patent/WO2007026018A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention is a solution of lithium aluminum hydride, a process for the preparation of this solution and their use.
  • Lithium aluminum hydride (LiAlH 4 ) is a strong reducing agent that dissolves well in polar solvents such as diethyl ether (Et 2 O) or tetrahydrofuran (THF). In the solid, powdery state, it is because of its high reactivity to air and
  • LiAlH 4 can be prepared by reacting an aluminum halide, in particular aluminum chloride (AICI3), with lithium hydride (LiH) in an ethereal one
  • AICI3 aluminum chloride
  • LiH lithium hydride
  • LiAlH 4 is very soluble in Et 2 O at 28%, but due to its low flame and boiling point, this solvent requires extensive safety measures. It is therefore avoided as much as possible in industrial applications.
  • LiAlH 4 solutions generally do not contain Et 2 O but are offered as a 10% solution in THF or a 15% solution in THF / toluene (Chemetall brochure "Industrial Use")
  • THF has a much higher boiling point as Et 2 O.
  • the boiling point of THF 66 0 C, of Et 2 O is only 35 ° C.
  • One possibility is the reaction of sodium aluminum hydride with lithium chloride (LiCl) (WO-A-97/06097):
  • LiAlH 4 THF solutions are prepared by dissolving solid, solvent-free LiAlH 4 in THF or THF / cosolvent.
  • the solid LiAlH 4 is synthesized in this case first as a solution in diethyl ether, which is then completely evaporated at higher temperatures and reduced pressure.
  • this method also has serious disadvantages. Initially, it is comparatively expensive due to its complexity. Furthermore, the thermal stress of LiAlH 4 on evaporation leads to a partial decomposition according to Scheme 3:
  • Li 3 AlH 6 is insoluble and therefore not useful for reduction processes.
  • the object of the present invention is to overcome the disadvantages of the prior art.
  • the present invention is intended to provide a LiAlH 4 solution which is as concentrated, safe to handle and inexpensive to obtain.
  • the objects are achieved by dissolving LiAlH 4 in 2-methyltetrahydrofuran (2-MeTHF) or a solvent mixture containing 2-methyltetrahydrofuran. Also preferred according to the invention is the preparation of LiAlH 4 in 2-MeTHF or a solvent mixture containing 2-MeTHF.
  • Powdered LiH is suspended in 2-MeTHF or a hydrocarbon or a 2-MeTHF / hydrocarbon mixture and a solution of AICI 3 in 2-MeTHF or a 2-MeTHF / hydrocarbon mixture is added to this suspension.
  • the grain size of LiH is preferably ⁇ 30 microns. The reaction is highly exothermic and the heat of reaction is removed by external cooling.
  • the reaction temperature is limited only by the solidification temperature in the lower region and by the boiling point of the solvent or solvent mixture used in the upper region. In practice, the reaction is carried out at temperatures between 0 0 C and 1 10 0 C. At higher temperatures is expected to begin product decomposition.
  • the preferred Reaction temperature is between 20 and 90 ° C. LiH is generally used in excess, preferably with an excess of 5 to 20%.
  • the by-produced LiCl is separated off.
  • This operation can be carried out according to the prior art by a solid / liquid separation step, for example by filtration, centrifugation or decantation. Preference is given to a filtrative work-up.
  • the filtrates are usually clear or slightly turbid, colorless or pale yellow. In particular, they are not contaminated by elemental aluminum. If the LiAlH 4 concentration is too low, they can be concentrated by evaporation, preferably in vacuo.
  • the LiCl solubility decreases markedly as the 2-MeTHF: LiAlH 4 ratio decreases.
  • a 2-MeOHF: LiAlH 4 ratio of 3.0 in the synthesis mixture and particularly preferably not exceed 2.2.
  • This can be achieved either by using concentrated AlCb solutions in pure 2-MeTHF or by using solvent mixtures.
  • aluminum chloride also dissolves well in mixtures of 2-MeTHF and a hydrocarbon.
  • the solubility of AICb in a mixture of 76% 2-MeTHF and 24% toluene is about 45%.
  • This solution has a 2-MeTHF: AICI 3 molar ratio of 1.5.
  • hydrocarbons preferably aromatic ones such as ethylbenzene, xylene, cumene or aliphatics such as cyclohexane, hexane, methylcyclohexane, heptane, alone or as a mixture of at least two of these solvents.
  • the synthesis is preferably carried out in a mixture of 2-MeOHF and a hydrocarbon, especially preferably a 2-MeTHF / toluene mixture.
  • a mixture of 2-MeOHF and a hydrocarbon especially preferably a 2-MeTHF / toluene mixture.
  • the molar ratio of 2-MeTHF should: AICI 3 3 not fall below a value of 1.
  • LiH is suspended in a hydrocarbon, for example toluene, and a solution of AICb in a 2-MeTHF hydrocarbon mixture, preferably in a 2-MeTHF / toluene mixture, is added.
  • a solution of AICb in a 2-MeTHF hydrocarbon mixture preferably in a 2-MeTHF / toluene mixture, is added.
  • the 2-MeTHF: AICI 3 ratio is between 1.3 and 3.0, preferably a 2-MeTHF: AlCb ratio of 1.5 to 2.0.
  • 2-MeTHF offers considerable advantages when used in the organic phase
  • 2-MeTHF-containing LiAlH 4 solutions have a particular thermal stability: in contrast to solutions in THF, they decompose endothermically. Therefore, no so-called “runaway” scenario is to be expected even at relatively high temperatures, which enables safe working even at high temperatures.
  • FIG. 1 The thermal stability of 2-MeTHF-containing LiAlH 4 solutions is illustrated in FIG. 1. This compares the results of differential scanning calometry tests in a Radex apparatus of a 12% solution of LiAlH 4 in 2-MeTHF / toluene with that of a 15% solution of LiAlH 4 in THF / toluene. In each case 2 g were weighed, the heating rate was 45 K / h.
  • Curve 1 12% solution of LiAlH 4 in 2-MeTHF / toluene: AT;
  • Curve 2 12% solution of LiAlH 4 in 2-MeTHF / toluene: pressure; Curve 3: 15% solution of LiAlH 4 in THF / toluene: AT;
  • Curve 4 15% solution of LiAlH 4 in THF / toluene: pressure.
  • LiAlH 4 a solution of LiAlH 4 in 2-MeTHF or a solvent mixture containing 2-MeTHF, the LiAlH 4 content being at least 14% by weight;
  • LiAlH 4 a solution of LiAlH 4 in 2-MeTHF or a solvent mixture containing 2-MeTHF, wherein the LiAlH 4 concentration is at least 5 wt% and the molar ratio of 2-MeTHF: LiAlH 4 is not 3.0 exceed;
  • aliphatic hydrocarbon is selected from cyclohexane, hexane, methylcyclohexane or heptane or a mixture of at least two of these hydrocarbons;
  • a process for the preparation of the LiAlH 4 solution according to the invention the concentration of LiH in the batch being between 3 and 17% by weight, preferably between 5 and 15% by weight; a process for producing the LiAlH 4 solution according to the invention, the LiH powder used having a particle size ⁇ 30 ⁇ m;
  • reaction temperature between 0 and 100 0 C, preferably between 20 and 90 0 C, more preferably between 30 and 80 ° C, is;
  • hydrocarbons are selected from toluene, ethylbenzene, xylene, cumene, cyclohexane, hexane, methylcyclohexane, heptane or a mixture of at least two of these hydrocarbons;
  • LiH powder 41.7 g are suspended in 40 g of 2-MeTHF in an inertized, that is dried and filled with inert gas, for example nitrogen or argon, in a 1 L jacketed reactor. It is heated to 35 ° C and added dropwise with good stirring, a solution of 158.7 g of AICb in 370 g of 2-MeTHF within 3 hours. After a 1, 5-hour post-reaction at 35 to 40 0 C, the reaction suspension is drained on a G3 glass filter.
  • inert gas for example nitrogen or argon
  • LiAlH 4 8.1% by weight (based on Al analysis)
  • LiCl 1, 6 wt.% ( ⁇ 17 mol%, based on Al)
  • Example 2 Preparation of a LiCl-poor LiAlhU solution in 2-MeTHF by an evaporation process
  • the LiAlH 4 concentration is 1 1, 4% ( ⁇ 98% of theory), the LiCl concentration in relation to LiAlH 4 at 1, 1 mol%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une solution d'hydrure d'aluminium et de lithium dans du 2-méthyltétrahydrofurane ou un mélange de solvant contenant du 2- méthyltétrahydrofurane, un procédé pour réaliser cette solution et son utilisation.
PCT/EP2006/065919 2005-09-01 2006-09-01 Solutions d'hydrure d'aluminium et de lithium Ceased WO2007026018A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN200680040697.9A CN101300192B (zh) 2005-09-01 2006-09-01 氢化铝锂溶液
EP06793144A EP1924524B1 (fr) 2005-09-01 2006-09-01 Procédé de préparation de solutions d'hydrure d'aluminium et de lithium
US11/991,132 US8840805B2 (en) 2005-09-01 2006-09-01 Solutions of lithium aluminum hydride

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102005041773.6 2005-09-01
DE102005041773 2005-09-01
DE102006028021.0 2006-06-14
DE102006028021 2006-06-14

Publications (1)

Publication Number Publication Date
WO2007026018A1 true WO2007026018A1 (fr) 2007-03-08

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PCT/EP2006/065919 Ceased WO2007026018A1 (fr) 2005-09-01 2006-09-01 Solutions d'hydrure d'aluminium et de lithium

Country Status (4)

Country Link
US (1) US8840805B2 (fr)
EP (1) EP1924524B1 (fr)
CN (1) CN101300192B (fr)
WO (1) WO2007026018A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110691A3 (fr) * 2010-03-12 2011-11-10 Chemetall Gmbh Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygène

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104725189A (zh) * 2014-12-09 2015-06-24 车荣睿 三叔丁氧基氢化铝锂的制备方法
CN104759215A (zh) * 2014-12-26 2015-07-08 车荣睿 一种氢化铝锂-四氢呋喃溶液的制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337308A (en) * 1964-02-19 1967-08-22 Foote Mineral Co Preparation of lithium aluminum hydride
WO1997006097A1 (fr) * 1995-08-09 1997-02-20 Fmc Corporation Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres
US20010051729A1 (en) * 1995-08-03 2001-12-13 Anne Pautard-Cooper Novel reduction compositions and processes for making the same
EP1394106A1 (fr) * 2002-08-16 2004-03-03 Chemetall GmbH Procédé pour la préparation de solutions d'hydrure double de lithium e d'aluminium

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6228338B1 (en) * 1999-06-16 2001-05-08 Sri International Preparation of aluminum hydride polymorphs, particularly stabilized α-alh3
CN1233546C (zh) * 2004-03-12 2005-12-28 山西大学 氢化铝锂的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337308A (en) * 1964-02-19 1967-08-22 Foote Mineral Co Preparation of lithium aluminum hydride
US20010051729A1 (en) * 1995-08-03 2001-12-13 Anne Pautard-Cooper Novel reduction compositions and processes for making the same
WO1997006097A1 (fr) * 1995-08-09 1997-02-20 Fmc Corporation Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres
EP1394106A1 (fr) * 2002-08-16 2004-03-03 Chemetall GmbH Procédé pour la préparation de solutions d'hydrure double de lithium e d'aluminium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110691A3 (fr) * 2010-03-12 2011-11-10 Chemetall Gmbh Solutions d'acides de lewis dans un solvant ou mélange de solvants contenant des donneurs d'oxygène
CN102939156A (zh) * 2010-03-12 2013-02-20 凯密特尔有限责任公司 在含氧供体的溶剂或溶剂混合物中的路易斯酸溶液

Also Published As

Publication number Publication date
EP1924524B1 (fr) 2012-11-14
EP1924524A1 (fr) 2008-05-28
CN101300192A (zh) 2008-11-05
US20090140201A1 (en) 2009-06-04
CN101300192B (zh) 2014-10-15
US8840805B2 (en) 2014-09-23

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